CN114762838A - Asymmetric coordination catalyst and preparation method and application thereof - Google Patents

Asymmetric coordination catalyst and preparation method and application thereof Download PDF

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CN114762838A
CN114762838A CN202110053595.7A CN202110053595A CN114762838A CN 114762838 A CN114762838 A CN 114762838A CN 202110053595 A CN202110053595 A CN 202110053595A CN 114762838 A CN114762838 A CN 114762838A
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ligand
acid
catalyst
metal
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CN114762838B (en
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纪勇强
易光铨
殷艳欣
万毅
孙康
黎源
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Wanhua Chemical Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention provides an asymmetric coordination catalyst and a preparation method and application thereof, the catalyst is an asymmetric coordination catalyst which takes VIB group or VIIIB group metals and compounds as active sites and two different VA group or VIA group non-metals as ligands, and the catalyst can show excellent activity and product selectivity; when the catalyst of the invention is used for the carbonylation reaction of the olefinic unsaturated compound, the product selectivity is high, the catalyst is easy to separate, and the cost is reduced.

Description

Asymmetric coordination catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to an asymmetric coordination catalyst for catalyzing carbonylation of an ethylenically unsaturated compound, and a preparation method and application thereof.
Background
The preparation of the corresponding esters or carboxylic acids by reaction of carbon monoxide with an olefinically unsaturated compound in an alcohol or water system using a catalyst system comprising a group VIII metal and a phosphine ligand such as an alkyl phosphine, cycloalkyl phosphine, aryl phosphine or bidentate phosphine, etc., is a common carbonylation reaction in which ethylene is carbonylated to the corresponding carboxylic acid or ester using carbon monoxide in an alcohol or water system.
Although relevant patent reports have developed a catalyst system with high activity, most of the conventional carbonylation reaction processes are homogeneous catalytic reactions, metal active sites are easily reduced and inactivated in the reaction process in the continuous operation process, the catalyst must be frequently supplemented, and the problem that the metal active sites are easily aggregated after being separated out and form mirror images on the wall of a reactor is found in the reaction process, so that the problems of difficult recovery, low recovery rate and high recovery cost are faced, and the problem of huge cost is faced in the industrial process.
Most of the existing catalysts for carbonylation of ethylenically unsaturated compounds are homogeneous catalysts, and the problem of catalyst and product separation during the completion of the reaction or continuous operation is generally realized by using a rectification mode. Patent EP- ｃA-0411721 reports ｃA separation process for the preparation of alkyl propionate whereby the condensed outlet product vapour stream is distilled by distillation to distill the alkyl propionate from the product stream azeotropically with the alkanol, and heavy components including the catalyst are returned to the reactor for further reaction, and separation of the product by distillation faces the following problems: firstly, the harsh conditions of rectification may cause irreversible damage to the catalyst to cause activity attenuation; secondly, the problems of increasing the construction cost of the device and increasing the energy consumption are faced in the industrial process, and the complexity of the reaction operation is increased.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide an asymmetric coordination catalyst with excellent catalytic activity, which reduces the loss of metal active sites during the reaction process, effectively improves the long-term stability of the catalyst, and makes the catalyst easier to separate and reduce the cost.
The invention also aims to provide a preparation method and application of the catalyst, and the catalyst is applied to carbonylation of ethylenically unsaturated compounds, has high catalytic activity and can effectively overcome the defects in the prior art.
In order to achieve the above object, the present invention adopts the following aspects.
An asymmetric coordination catalyst, comprising:
a) a group VIB or group VIIIB metal active component;
b) a first ligand;
c) a second ligand;
d) and (3) a carrier.
The first ligand and the second ligand are different and are nonmetal coordinators of VA family or VIA family, preferably, nonmetal elements of VA family or VIA family in the second ligand are different from nonmetal elements of VA family or VIA family in the first ligand.
Wherein the group VIB or VIIIB metal comprises one or more metals selected from Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt and Pd, preferably selected from Ni, Pt and Pd; the non-metal ligand of the VA group or the VIA group comprises one or more of N, P, As, O, S, Se and Te elements, preferably, the non-metal of the VA group or the VIA group is one or more selected from N, P, O and S elements; the carrier is a carbon carrier, including but not limited to carbon nanofibers, carbon nanotubes, carbon nanosheets, graphene, carbon foams or the like.
The nonmetal compatible ligand of VA family or VIA family is selected from heterocycle and aromatic compound containing VA family or VIA family elements and carboxylic acid, sulfonic acid and amino substituent thereof, or corresponding alkyl, cycloalkyl, aryl or bidentate nonmetal ligand. Preferably, the nitrogen-containing ligands include, but are not limited to, pyridine, 2 '-bipyridine, 4' -bipyridine, and the like, the phosphorus-containing ligands include, but are not limited to, triphenylphosphine, trimethylphosphine, bis (diphenylphosphino) methane, and the like, the sulfur-containing ligands include, but are not limited to, thiophenol, thiol, and the like, and the oxygen-containing ligands include, but are not limited to, 1, 2-phenylenedioxydiacetic acid, diphenylglycolic acid, and the like.
In some preferred embodiments of the invention, the first ligand is an N-containing ligand and the second ligand is an P, O-or S-containing ligand.
In some preferred embodiments of the invention, the first ligand is a P-containing ligand and the second ligand is N, O-or S-containing ligand.
In some preferred embodiments of the present invention, the catalyst is prepared by:
firstly, preprocessing a carrier;
dissolving a VIB group or VIIIB group metal active component precursor, a first ligand and a second ligand in an organic solvent, stirring and mixing uniformly, adding the pretreated carrier, heating to a certain temperature for reaction, and then washing and drying;
thirdly, roasting the catalyst prepared in the second step in an inert gas atmosphere.
In some preferred embodiments of the present invention, the catalyst may also be prepared by:
A) pretreating the carrier;
B) dissolving a VIB group or VIIIB group metal active component precursor and a first ligand in an organic solvent, stirring and mixing uniformly, adding the pretreated carrier, heating to a certain temperature for reaction, and then washing and drying.
C) Carrying out gas etching on the catalyst prepared in the step B) in an etching gas atmosphere.
The pretreatment method of the carrier adopts a known method for pretreatment such as a hydrothermal method, a template method, a self-assembly technology and the like, or is directly purchased through commercial products, the carbon carrier is pretreated by technologies including but not limited to acid washing, plasma etching or anodic oxidation and the like so as to increase the amorphous degree of the carbon carrier, the defect sites of the carbon carrier anchor a catalyst system, the uniform distribution of the catalyst system is realized, and the problem of activity reduction of the catalyst system caused by the agglomeration of electrostatic interaction in the reaction process is avoided.
In some preferred embodiments of the present invention, the carrier is pretreated by acid washing, preferably one or more of oxyacids such as nitric acid, concentrated sulfuric acid, permanganic acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid, and more preferably one or more of nitric acid, concentrated sulfuric acid, permanganic acid, and nitrous acid; preferably the acid concentration is from 10 wt% to 100 wt%, more preferably from 30 wt% to 80 wt%; the mass ratio of the acid to the carbon carrier is preferably 1: 1-100: 1, preferably 10: 1-50: 1; the pickling process is preferably carried out for 1 to 8 hours at a temperature of between 30 and 150 ℃, and more preferably for 3 to 5 hours at a temperature of between 50 and 100 ℃. Preferably, the pretreated carrier is washed by water until the washing liquid is neutral, and then is dried, wherein the drying temperature and the drying time have no special requirements, preferably the drying temperature is 50-150 ℃, and the drying time is based on complete drying.
The mass ratio of the carrier added in the step (II) to the metal elements in the VIB group or VIIIB group metal active component precursor is 10: 1-500: 1, preferably 100: 1-200: 1; the mass concentration of the VIB group or VIIIB group metal active component precursor in the methanol solution is preferably 0.01-1.0 wt%.
The VIB group or VIIIB group metal active component precursor is a VIB group or VIIIB group metal compound, and comprises salts (organic salts and inorganic salts) of the metals or weak-coordination anionic compounds derived from the following acids: nitric acid, sulfuric acid, sulfonic acid, phosphoric acid, carboxylic acid, perhalogenic acid, lewis acid, and bronsted acid derived from each other, and the like.
The first ligand and the second ligand are different and are respectively selected from corresponding heterocyclic rings, aromatic compounds and carboxylic acid, sulfonic acid and amino substituent of non-metal in VA family or VIA family, or corresponding alkyl, cycloalkyl, aryl or bidentate non-metal ligand, preferably, the first ligand and the second ligand are respectively selected from one or more of nitrogen, phosphorus, oxygen and sulfur.
In the invention, the molar ratio of the total molar amount of the VA group or VIA group nonmetal in the first ligand and the second ligand to the metal element in the VIB group or VIIIB group metal active component precursor is 2: 1-20: 1, preferably 2: 1-10: 1, so as to ensure the saturated coordination of the metal active site, enhance the binding force between the coordinatable body and the metal active site and ensure the firmness of the metal active site. Preferably, the molar ratio of the molar amount of the VA group or VIA group nonmetal in the first ligand to the molar amount of the metal in the VIB group or VIIIB group metal active component precursor is 1: 1-10: 1, preferably 1: 1-5: 1, the molar quantity of the VA group or VIA group nonmetal and the molar quantity of the VIB group or VIIIB group metal active component precursor in the second ligand are 1: 1-10: 1, preferably 1: 1-5: 1.
the reaction temperature of the step II and the step B) is 80-120 ℃, and the reaction time is preferably 5-10 h; the drying temperature is preferably 50-150 deg.C, and the drying time is based on complete drying.
In the step (c), the roasting temperature of the catalyst is preferably 600-1200 ℃, and more preferably 800-1000 ℃; the roasting time is not easy to be overlong, and is preferably 1 to 5 hours, and more preferably 2 to 4 hours.
In the step C), the etching gas includes a second ligand, and the second ligand which can be coordinated by a gas etching method is a non-metal compound of group va or group via which gas or vapor is generated at the etching temperature, such as a non-metal hydrogen compound selected from group va or group via, e.g., ammonia, phosphine, hydrogen sulfide, or water, or an acid containing a non-metal of group va or group via, e.g., nitric acid, phosphoric acid, or sulfuric acid, or an organic compound containing a non-metal of group va or group via, e.g., amines, sulfonic acids, phosphorus compounds, and carboxylic acid compounds.
The etching gas also comprises inert gas, and the volume concentration of the second ligand gas in the etching gas is 10% -50%, preferably 20% -40%.
The etching temperature is 600-1200 ℃, preferably 800-1000 ℃, and the etching time is 1-5h, preferably 2-4 h.
If the gas etching method is selected to coordinate the second ligand and the metal, the roasting is not needed.
The metal active component formed by the method is anchored on the ligand of asymmetric coordination and is fixed in the carbon hoop formed after the organic ligand is roasted or etched, the problem of electrostatic adsorption agglomeration caused by volume effect is avoided, the metal active component is uniformly distributed on the surface of the carrier, the asymmetric coordination structure enables the metal active site to show asymmetric migration of electron cloud under the electronegativity effect of the metal active site, more active sites are released, and the catalyst can show excellent catalyst activity and product selectivity.
The invention also provides the use of the asymmetric coordination catalyst in catalyzing the carbonylation of an ethylenically unsaturated compound.
A process for the carbonylation of an ethylenically unsaturated compound comprising reacting an ethylenically unsaturated compound with carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst as described herein.
The hydroxyl-containing compound is water or a hydroxyl-functional organic molecule, which may be linear or branched and comprises alkanols, aryl alkanols, preferably C1-C8 alkanols, more preferably methanol and ethanol, even more preferably methanol, optionally substituted with one or more substituents of lower alkyl, halogen, nitro or cyano. The adding amount of the hydroxyl-containing compound can be reasonably adjusted according to the reaction type, and preferably, the molar ratio of the adding amount of the hydroxyl-containing compound to the ethylenically unsaturated compound is 1: 0.1-1: 10. more preferably 1: 1-1: 0.1.
the carbon monoxide may be used in pure form or diluted with an inert gas such as nitrogen, argon, etc., and a small amount of hydrogen less than 5% by volume may also be present. The molar ratio of olefinically unsaturated compound to carbon monoxide is preferably 1: 1-10: 1.
the amount of the catalyst can be added according to the common knowledge in the field, and the molar amount of the active component of the metal in the VIB group or the VIIIB group in the catalyst is preferably 10 mol of the molar amount of the hydroxyl-containing compound-5To 10-3Double, preferably 10-4To 5X 10-4And (4) doubling.
The carbonylation of ethylenically unsaturated compounds of the present invention may be carried out in one or more reaction-inert solvents, suitable solvents include ketones, ethers, esters, amides and aromatics and the like and derivatives thereof, preferably at 298.15K and 1 x 105Nm-2An aprotic solvent having a lower dielectric constant in the range of 3 to 8, preferably anisole as a reaction solvent, and preferably in a volume ratio of solvent to hydroxyl group-containing compound of 1: 1-10: 1, the reaction is preferably carried out in the absence of an added aprotic solvent.
The ethylenically unsaturated compounds include straight or branched chain alkenes or alkynes containing one or more unsaturated bonds, preferably 1 to 3 unsaturated bonds, which may be unsubstituted or substituted with alkyl, aryl, heteroatom containing groups, and the like.
The carbonylation reaction is carried out at 0-150 ℃, and the preferable reaction temperature is 50-100 ℃; the reaction pressure is 0-10MPa, preferably 0.5-2 MPa.
According to the olefinic unsaturated compound carbonylation catalyst prepared by the invention, VIB group or VIIIB group metal is used as an active site, and VA group or VIA group heteroatom is used as a nonmetal coordinatable body and is anchored on the surface of a carbon carrier, so that the catalyst has excellent structural stability, the loss of the metal active site in the reaction process can be effectively reduced, the catalyst loss is reduced, the long-period stability of the catalyst is improved, and on the other hand, the recovery rate of the catalyst can be effectively improved, and the recovery cost of the catalyst is reduced. Meanwhile, the nonmetal ligand adopts two different ligands to coordinate metals to form an asymmetric structure, the asymmetric structure can enable the active site of the metal to show asymmetric migration of electron cloud under the electronegativity effect, more active sites are released, and the catalyst can show excellent catalyst activity and product selectivity.
In addition, the catalyst prepared according to the invention can realize product separation through simple filtration, thereby providing convenience for continuous or intermittent long-period operation and reducing the separation cost.
Detailed description of the invention
The invention determines the metal loading capacity through ICP, and determines the coordination amount of nonmetal in the nonmetal ligand through fluorescence and nuclear magnetism, so as to determine the composition condition of the prepared catalyst.
The invention analyzes the product by gas chromatography, calculates the reaction conversion number TON by the following formula, compares the catalyst activity by TON:
TON ═ mol of molar amount of methyl propionate formed during the reaction/mol of molar amount of metal added
The following examples further illustrate preferred embodiments within the scope of the present invention, which are intended to be illustrative only and not to be limiting in scope, and are intended to further describe and show embodiments within the scope of the present invention, and therefore, the examples should be construed as merely illustrative in more detail and not limitative of the remainder of the disclosure in any way whatsoever.
Example 1
Pretreatment of a carrier:
adding 35g of carbon nano tube into 200g of nitric acid solution with the mass fraction of 50 wt%, heating and refluxing for 4h at 80 ℃, cooling, washing with a large amount of clear water until the washing liquid is neutral, and transferring the acid-treated carbon carrier into a forced air drying oven to dry for 12h at 105 ℃ for later use.
Adding 5g of graphene into 200g of nitric acid solution with the mass fraction of 50 wt%, treating for 4h under the condition of heating reflux at 80 ℃, cooling, washing with a large amount of clear water until the washing liquid is neutral, and transferring the acid-treated carbon carrier into a forced air drying oven to dry for 12h at 105 ℃ for later use.
Adding 5g of carbon nano-sheets into 200g of nitric acid solution with the mass fraction of 50 wt%, treating for 4h under the condition of heating and refluxing at 80 ℃, cooling, washing with a large amount of clear water until the washing liquid is neutral, and transferring the acid-treated carbon carrier into a forced air drying oven to dry for 12h at 105 ℃ for later use.
Example 2
Dissolving 0.1g of palladium acetate, 0.0352g of pyridine and 0.1168g of triphenylphosphine in 50g of methanol, stirring and mixing uniformly, adding 4.7g of the carbon nanotube prepared in example 1, transferring to a reaction kettle, heating to 100 ℃ under normal pressure, reacting for 8h, standing, cooling, taking out, washing with a large amount of methanol, placing the washed catalyst in an oven, drying at 100 ℃ for 5h, transferring to a muffle furnace, roasting at 900 ℃ for 3h, taking out and evaluating.
And (3) carrying out carbonylation reaction on the prepared catalyst: dissolving 0.1g of catalyst in 500ml of dehydrated and deoxidized methanol under the anaerobic condition, transferring the catalyst into a 1L reaction kettle, replacing gas in the kettle with ethylene, heating to 80 ℃, and introducing a catalyst with a molar ratio of 1: 1 to 1MPa, and reacting the ethylene and the carbon monoxide in a molar ratio of 1: 1, maintaining the pressure of inlet air at 1MPa, recording the instantaneous air inflow of the reaction to reflect the instantaneous reaction rate, stopping the reaction when the air inflow rate is zero, recording the total air inflow, taking a certain amount of liquid after the reaction kettle is cooled, performing product analysis by gas chromatography, and calculating the reaction conversion number TON, wherein the TON is 20.1w, and the molar selectivity of the methyl propionate is 99.5%.
Example 3
Dissolving 0.1g of palladium acetate and 0.1168g of triphenylphosphine in 50g of methanol, stirring and mixing uniformly, adding 4.7g of graphene prepared in example 1, transferring the mixture into a reaction kettle, heating the mixture to 120 ℃ under normal pressure, reacting for 5 hours, standing and cooling the mixture, taking the mixture out, and washing the mixture with a large amount of methanol
Placing the washed catalyst in an oven, drying at 50 ℃ for 10h, transferring into a tube furnace, etching at 800 ℃ for 4h in the atmosphere of mixed gas of helium and ammonia (the volume fraction of ammonia is 20 vol%), and testing the ratio of the coordination molar quantity of the nitrogen element to the molar quantity of the metal palladium to reach 1: after 1, cooling, taking out the product, and carrying out activity evaluation according to the evaluation method in example 2, and calculating the conversion number of the reaction, wherein the TON is 25.3w, and the molar selectivity of the product methyl propionate is 99.8 percent
Example 4
Dissolving 0.1g of palladium acetate and 0.07g of pyridine in 50g of methanol, stirring and mixing uniformly, adding 4.7g of the carbon nanosheet prepared in the example 1, transferring to a reaction kettle, heating to 80 ℃ under normal pressure, reacting for 10h, standing, cooling, taking out, and washing with a large amount of methanol.
Placing the washed catalyst in an oven, drying at 150 ℃ for 2h, transferring into a tubular furnace, etching at 1000 ℃ for 2h in the atmosphere of a mixed gas of helium and phosphine (the volume fraction of phosphine is 20 vol%), and testing that the coordination molar quantity of phosphine and the molar quantity of metal palladium reach 2 by fluorescence and nuclear magnetism: after 1, the reaction mixture was cooled and then taken out for activity evaluation according to the evaluation method in example 2, and the conversion number of the reaction was calculated, wherein TON was 22.8w, and the molar selectivity of the methyl propionate product was 99.8%.
Example 5
Dissolving 0.1g of palladium acetate, 0.0491g of thiophenol and 0.0339g of diphenylglycolic acid in 50g of methanol, stirring and mixing uniformly, adding 4.7g of the carbon nano tube prepared in the example 1, transferring to a reaction kettle, heating to 100 ℃ under normal pressure, reacting for 8 hours, standing, cooling, taking out, washing with a large amount of methanol, placing the washed catalyst in an oven, drying at 100 ℃ for 5 hours, transferring to a muffle furnace, roasting at 900 ℃ for 3 hours, taking out and evaluating.
The carbonylation reaction was fed in the same manner as in example 2, and the conversion of the reaction was calculated to be 23.5w, and the molar selectivity of the methyl propionate product was 99.5%.
Comparative example 1
Dissolving 0.1g of palladium acetate and 0.0704g of pyridine in 50g of methanol, stirring and mixing uniformly, adding 4.7g of the carbon nano tube prepared in the embodiment 1, transferring the mixture into a reaction kettle, heating the mixture to 100 ℃ under normal pressure, reacting for 8h, standing and cooling, taking out the mixture, washing the mixture with a large amount of methanol, putting the washed catalyst into an oven, drying the catalyst at 100 ℃ for 5h, transferring the dried catalyst into a muffle furnace, roasting the roasted catalyst at 900 ℃ for 3h, cooling, taking out the catalyst, performing carbonylation reaction according to the method in the embodiment 2, calculating the reaction conversion number, wherein the TON is 10.0w, and the molar selectivity of the methyl propionate is 98.5%.
Comparative example 2
Dissolving 0.1g of palladium acetate and 0.2336g of triphenylphosphine in 50g of methanol, stirring and mixing uniformly, adding 4.7g of the carbon nano tube prepared in the embodiment 1, transferring the mixture into a reaction kettle, heating the mixture to 100 ℃ under normal pressure, reacting for 8h, standing and cooling, taking out the mixture, washing the mixture with a large amount of methanol, putting the washed catalyst into a drying oven, drying the catalyst at 100 ℃ for 5h, transferring the dried catalyst into a muffle furnace, roasting the catalyst at 900 ℃ for 3h, cooling, taking out the catalyst, performing carbonylation reaction according to the method in the embodiment 2, calculating the reaction conversion number, wherein the TON is 12.0w, and the molar selectivity of the methyl propionate is 98.0%.
Comparative example 3
Dissolving 0.1g of palladium acetate and 0.0982g of thiophenol in 50g of methanol, stirring and mixing uniformly, adding 4.7g of the carbon nano tube prepared in the example 1, transferring the mixture into a reaction kettle, heating the mixture to 100 ℃ under normal pressure, reacting for 8h, standing and cooling, taking out the mixture, washing the mixture with a large amount of methanol, putting the washed catalyst into a drying oven, drying the catalyst at 100 ℃ for 5h, transferring the dried catalyst into a muffle furnace, roasting the roasted catalyst at 900 ℃ for 3h, cooling, taking out the catalyst, performing activity evaluation according to the evaluation method in the example 2, calculating the conversion number of the reaction, wherein the TON is 10.8w, and the molar selectivity of the methyl propionate is 97.3%.
Comparative example 4
Dissolving 0.1g of palladium acetate and 0.0678g of diphenylglycolic acid in 50g of methanol, stirring and mixing uniformly, adding 4.7g of the carbon nano tube prepared in the embodiment 1, transferring the mixture into a reaction kettle, heating the mixture to 100 ℃ under normal pressure, reacting for 8h, standing and cooling, taking out the mixture, washing the mixture by using a large amount of methanol, putting the washed catalyst into a drying oven, drying the catalyst at 100 ℃ for 5h, transferring the dried catalyst into a muffle furnace, roasting the roasted catalyst at 900 ℃ for 3h, cooling, taking out the catalyst, performing activity evaluation according to the evaluation method in the embodiment 2, calculating the conversion number of the reaction, wherein the TON is 14.6w, and the molar selectivity of the methyl propionate is 95.1%.
By comparing the asymmetric complex catalysts of ethylenically unsaturated compounds prepared in the above examples and comparative examples, it is possible to obtain a catalyst prepared by the present patent which can exhibit excellent catalytic activity, more excellent product selectivity and long-term stability on the one hand. On the other hand, the specific catalyst structure ensures that the structure is stable, the loss of metal active sites in the reaction process can be effectively reduced, the recovery rate of the catalyst metal is improved, and the recovery cost is reduced. In addition, the catalyst prepared according to the invention can realize product separation through simple filtration, thereby providing convenience for continuous or intermittent long-period operation and reducing the separation cost.

Claims (10)

1. An asymmetric coordination catalyst, wherein said catalyst comprises:
a) a VIB group or VIIIB group metal active component;
b) a first ligand;
c) a second ligand;
d) a carrier;
the first ligand and the second ligand are different and are nonmetal coordinators of VA family or VIA family, preferably, nonmetal elements of VA family or VIA family in the second ligand are different from nonmetal elements of VA family or VIA family in the first ligand;
wherein the group VIB or VIIIB metal comprises one or more metals selected from Cr, Mo, W, Fe, Co, Ni, Ru, Rh, Os, Ir, Pt and Pd, preferably selected from Ni, Pt and Pd; the non-metal ligand of the VA group or the VIA group comprises one or more of N, P, As, O, S, Se and Te elements, preferably, the non-metal of the VA group or the VIA group is one or more selected from N, P, O and S elements; the support is a carbon support, including but not limited to carbon nanofibers, carbon nanotubes, carbon nanoplatelets, graphene, or carbon foam.
2. The asymmetric coordination catalyst according to claim 1, wherein the non-metallic group va or group via ligands are selected from the group consisting of heterocycles comprising group va or group via elements, aromatics and their carboxylic, sulfonic and amine group substituents, or the corresponding alkyl, cycloalkyl, aryl or bidentate non-metallic ligands; preferably, the nitrogen-containing ligands include, but are not limited to, pyridine, 2 '-bipyridine, and 4, 4' -bipyridine, the phosphorus-containing ligands include, but are not limited to, triphenylphosphine, trimethylphosphine, and bis (diphenylphosphine) methane, the sulfur-containing ligands include, but are not limited to, thiophenol and thiol, and the oxygen-containing ligands include, but are not limited to, 1, 2-phenylenedioxydiacetic acid and diphenylglycolic acid;
preferably, the first ligand is an N-containing ligand and the second ligand is an P, O-or S-containing ligand;
preferably, the first ligand is a P-containing ligand and the second ligand is a N, O or S-containing ligand.
3. The method for preparing an asymmetric coordination catalyst according to claim 1, comprising the steps of:
firstly, preprocessing a carrier;
dissolving a VIB group or VIIIB group metal active component precursor, a first ligand and a second ligand in an organic solvent, stirring and mixing uniformly, adding the pretreated carrier, heating to a certain temperature for reaction, and then washing and drying;
and thirdly, roasting the catalyst prepared in the second step in an inert gas atmosphere.
4. The method for preparing an asymmetric coordination catalyst according to claim 1, comprising the steps of: A) pretreating the carrier;
B) dissolving a VIB group or VIIIB group metal active component precursor and a first ligand in an organic solvent, stirring and mixing uniformly, adding a pretreated carrier, heating to a certain temperature for reaction, and then washing and drying;
C) carrying out gas etching on the catalyst prepared in the step B) in an etching gas atmosphere.
5. The method for preparing an asymmetric coordination catalyst according to claim 3 or 4, wherein the carrier is pretreated by acid washing, preferably one or more of oxygen acids such as nitric acid, concentrated sulfuric acid, permanganic acid, hypochlorous acid, chloric acid, chlorous acid, perchloric acid, nitrous acid, and more preferably one or more of nitric acid, concentrated sulfuric acid, permanganic acid, and nitrous acid; preferably the acid concentration is from 10 wt% to 100 wt%, more preferably from 30 wt% to 80 wt%;
preferably, the mass ratio of acid to carbon support is 1: 1-100: 1, more preferably in a mass ratio of 10: 1-50: 1; the pickling process is preferably carried out for 1 to 8 hours at a temperature of between 30 and 150 ℃, and more preferably for 3 to 5 hours at a temperature of between 50 and 100 ℃.
6. The preparation method of the asymmetric coordination catalyst according to claim 3 or 4, wherein the mass ratio of the carrier added in the step (II) and the step (B) to the metal elements in the VIB group or VIIIB group metal active component precursor is 10: 1-500: 1, preferably 100: 1-200: 1;
the VIB group or VIIIB group metal active component precursor is a VIB group or VIIIB group metal compound, and comprises salts of the metals or weak coordination anionic compounds derived from the following acids: nitric acid, sulfuric acid, sulfonic acid, phosphoric acid, carboxylic acid, perhalogenic acid, lewis acid, and bronsted acid;
preferably, the molar ratio of the total molar amount of the VA or VIA non-metal in the first ligand and the second ligand to the metal element in the VIB or VIIIB metal active component precursor is 2: 1-20: 1, preferably 2: 1-10: 1;
preferably, the molar ratio of the molar amount of the VA group or VIA group nonmetal in the first ligand to the molar amount of the metal in the VIB group or VIIIB group metal active component precursor is 1: 1-10: 1, preferably 1: 1-5: 1;
preferably, the molar amount of the group VA or group VIA nonmetal in the second ligand and the molar amount of the group VIB or group VIIIB metal active component precursor in the second ligand are 1: 1-10: 1, preferably 1: 1-5: 1.
7. the method for preparing the asymmetric coordination catalyst according to claim 3 or 4, characterized in that the reaction temperature of the step (II) and the step (B) is 80-120 ℃, and the reaction time is preferably 5-10 h; the drying temperature is preferably 50-150 ℃;
preferably, in the step (c), the calcination temperature of the catalyst is preferably 600-1200 ℃, and more preferably 800-1000 ℃; the calcination time is 1-5h, more preferably 2-4 h.
8. The method for preparing the asymmetric coordination catalyst according to claim 4, wherein in the step C), the etching gas comprises a second ligand, and the second ligand capable of being coordinated by gas etching is a nonmetallic compound of group VA or group VIA which is gas or vapor under the condition of etching temperature;
preferably, the second ligand is selected from non-metallic hydrogen compounds of group VA or VIA, preferably ammonia gas, phosphine, hydrogen sulfide or water, or non-metallic acids containing group VA or VIA, preferably nitric acid, phosphoric acid and sulfuric acid, or non-metallic organic compounds containing group VA or VIA, preferably amines, sulfonic acids, phosphorus compounds and carboxylic acid compounds;
preferably, the etching gas further comprises an inert gas, and the volume concentration of the second ligand gas in the etching gas is 10% -50%, preferably 20% -40%;
preferably, the etching temperature is 600-1200 ℃, preferably 800-1000 ℃, and the etching time is 1-5h, preferably 2-4 h.
9. Use of a catalyst according to claims 1 to 2 or prepared according to the preparation process of claims 3 to 8 for catalysing the carbonylation of an ethylenically unsaturated compound.
10. A process for the carbonylation of an ethylenically unsaturated compound comprising reacting an ethylenically unsaturated compound with carbon monoxide and a hydroxyl group containing compound in the presence of a catalyst as claimed in claims 1 to 2 or prepared by the process of claims 3 to 8;
preferably, the molar ratio of the added hydroxyl-containing compound to the ethylenically unsaturated compound is 1: 0.1-1: 10, more preferably 1: 1-1: 0.1;
preferably, the molar ratio of the olefinically unsaturated compound to carbon monoxide is preferably from 1: 1-10: 1;
preferably, the molar weight of the active component of the metal in the VIB group or the VIIIB group in the catalyst is 10 of the molar weight of the hydroxyl-containing compound-5To 10-3Double, preferably 10-4To 5X 10-4Doubling;
preferably, the carbonylation reaction is carried out at 0-150 ℃, preferably at 50-100 ℃; the reaction pressure is 0-10MPa, preferably 0.5-2 MPa.
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JPH08299803A (en) * 1995-03-07 1996-11-19 Daicel Chem Ind Ltd Carbonylation catalyst and carbonylation method using the same
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WO2017025593A1 (en) * 2015-08-12 2017-02-16 Basf Se Catalyst comprising a phosphide-containing active component and method for insertion of carbon monoxide in reactant components
JP2018024631A (en) * 2016-07-28 2018-02-15 エヌ・イーケムキャット株式会社 Method of obtaining carbonyl compound by carbonylation reaction of halogen compound using aldehyde as carbon monoxide source in presence of heterogenous palladium catalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1127245A (en) * 1994-07-22 1996-07-24 大世吕化学工业株式会社 Catalytic systems and methods for carbonylation
JPH08299803A (en) * 1995-03-07 1996-11-19 Daicel Chem Ind Ltd Carbonylation catalyst and carbonylation method using the same
CN103691451A (en) * 2014-01-07 2014-04-02 中国科学院福建物质结构研究所 Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst
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